JP2001316686A - Sliding member with hard carbon film - Google Patents

Sliding member with hard carbon film

Info

Publication number
JP2001316686A
JP2001316686A JP2000131750A JP2000131750A JP2001316686A JP 2001316686 A JP2001316686 A JP 2001316686A JP 2000131750 A JP2000131750 A JP 2000131750A JP 2000131750 A JP2000131750 A JP 2000131750A JP 2001316686 A JP2001316686 A JP 2001316686A
Authority
JP
Japan
Prior art keywords
carbon film
sliding member
hard carbon
oil
lubricating oil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP2000131750A
Other languages
Japanese (ja)
Other versions
JP4007440B2 (en
Inventor
Shojiro Miyake
宅 正二郎 三
Yoshiteru Yasuda
田 芳 輝 保
Yutaka Mabuchi
渕 豊 馬
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nissan Motor Co Ltd
Original Assignee
Nissan Motor Co Ltd
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Filing date
Publication date
Application filed by Nissan Motor Co Ltd filed Critical Nissan Motor Co Ltd
Priority to JP2000131750A priority Critical patent/JP4007440B2/en
Publication of JP2001316686A publication Critical patent/JP2001316686A/en
Application granted granted Critical
Publication of JP4007440B2 publication Critical patent/JP4007440B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Landscapes

  • Valve-Gear Or Valve Arrangements (AREA)
  • Sliding-Contact Bearings (AREA)
  • Lubricants (AREA)
  • Physical Vapour Deposition (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a sliding member with a hard carbon film excellent in low friction and low abrasion in a lubricating oil. SOLUTION: This sliding member with a hard carbon film used in a lubricating oil is prepared by forming a hard carbon film 12 on a backing 11, wherein at least the surface layer of the film 12 contains 5-70 atm.% of at least one metal element selected from the group consisting of group IIb, III, IV, Va, VIa, VIIa and VIII elements in the periodic table.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、硬質炭素皮膜摺動
部材、特に、エンジンオイル，トランスミッションオイ
ル等の潤滑油中で使用される低摩擦な硬質炭素皮膜摺動
部材に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hard carbon film sliding member, and more particularly to a low friction hard carbon film sliding member used in lubricating oils such as engine oil and transmission oil.

【０００２】[0002]

【従来の技術】硬質炭素皮膜は、アモルファス状の炭素
膜あるいは水素化炭素膜で、ａ−Ｃ：Ｈ（アモルファス
カーボンまたは水素化アモルファスカーボン），ｉ−Ｃ
（アイカーボン），ＤＬＣ（ダイヤモンドライクカーボ
ンまたはディ−エルシ−）とも呼ばれている。2. Description of the Related Art A hard carbon film is an amorphous carbon film or a hydrogenated carbon film, and includes aC: H (amorphous carbon or hydrogenated amorphous carbon), iC
(Eye carbon) and DLC (diamond-like carbon or DLC).

【０００３】その形成には、炭化水素ガスをプラズマ分
解して成膜するプラズマＣＶＤ法や、炭素，炭化水素イ
オンを用いるイオンビーム蒸着法等の気相合成法や、グ
ラファイト等をアーク放電により蒸発させ成膜するイオ
ンプレーティング法、などが用いられる。[0003] The formation is performed by a plasma CVD method for forming a film by decomposing a hydrocarbon gas into a plasma, a gas phase synthesis method such as an ion beam evaporation method using carbon or hydrocarbon ions, or a method of evaporating graphite or the like by arc discharge. For example, an ion plating method of forming a film by deposition is used.

【０００４】硬質炭素皮膜は高硬度で、表面が平滑で耐
摩擦性に優れ、その固体潤滑性から低摩擦係数で優れた
低摩擦性能を有している。そして、通常の平滑な鋼材表
面の摩擦係数が無潤滑下で０．５〜１．０であるのに対
し、硬質炭素膜は無潤滑下での摩擦係数が０．１程度で
ある。The hard carbon film has a high hardness, a smooth surface and excellent friction resistance, and has a low friction coefficient and excellent low friction performance due to its solid lubricity. The friction coefficient of a normal smooth steel surface is 0.5 to 1.0 without lubrication, whereas the hard carbon film has a friction coefficient of about 0.1 without lubrication.

【０００５】現在、これらの優れた特性を活かして、ド
リル刃をはじめとする切削工具，研削工具等の加工治具
や塑性加工用金型、バルブコックやキャプスタンローラ
のような無潤滑下での摺動部品等への応用が図られてい
る。At present, by taking advantage of these excellent characteristics, it is possible to use a cutting tool such as a drill bit and a grinding tool, a jig for plastic working, a mold for plastic working, a valve cock, a capstan roller and the like without lubrication. Are being applied to sliding parts and the like.

【０００６】また、潤滑油中で摺動する内燃機関などの
機械部品においても、エネルギー消費や環境問題の面か
らできるだけ機械損失を低減したいという要求が高まっ
ており、特に、摩擦損失の大きい摺動条件の厳しい部位
で、これらの固体潤滑性を有する硬質炭素皮膜による低
摩擦化が望まれている。[0006] In mechanical parts such as internal combustion engines that slide in lubricating oil, there is a growing demand for reducing mechanical loss as much as possible from the viewpoint of energy consumption and environmental problems. It is desired that the hard carbon film having the solid lubricating property reduce the friction in a site where conditions are severe.

【０００７】[0007]

【発明が解決しようとする課題】しかしながら、従来の
上記硬質炭素膜を摺動部品にコーティングし、エンジン
油やトランスミッション油等の潤滑油中で摺動させた場
合、その平滑性からある程度の低摩擦とはなるが、他の
固体潤滑性を有していない硬質の皮膜処理をした摺動部
材、たとえば窒化チタン（ＴｉＮ）や窒化クロム（Ｃｒ
Ｎ）イオンプレーティング皮膜処理を施した摺動部材と
同等の低摩擦性能しか示さないという問題点が明らかに
なった。すなわち、従来の硬質炭素皮膜処理された摺動
部材では、無潤滑下で固体潤滑性があるにもかかわら
ず、同等の表面粗さの固体潤滑性を有しない皮膜処理摺
動部材や超仕上げ加工された鋼製部品と同等の摩擦性能
しか示さないという問題が明らかになった。However, when the conventional hard carbon film is coated on a sliding part and slid in a lubricating oil such as an engine oil or a transmission oil, a certain low friction is required due to its smoothness. However, other hardened sliding members having no solid lubricating properties, such as titanium nitride (TiN) and chromium nitride (Cr
N) The problem that only a low friction performance equivalent to that of the sliding member subjected to the ion plating film treatment was revealed. That is, conventional sliding members treated with a hard carbon film have a solid lubricating property without lubrication, but do not have a solid lubricating property with the same surface roughness or super finish processing. The problem has been clarified that it shows only the same frictional performance as that of the manufactured steel parts.

【０００８】たとえば、潤滑油中で３／８インチボール
３個を１ｋｇｆの荷重で押し付け、０．０３ｍ／ｓｅｃ
の相対速度で滑らせた場合、硬質炭素膜であるダイヤモ
ンドライクカーボンの摩擦係数は０．１０〜０．１２
で、同等の表面粗さで皮膜処理をしない鉄鋼材や、ある
いは、窒化クロム（ＣｒＮ）イオンプレーティング処理
膜と潤滑油中では同等の摩擦係数である。[0008] For example, three 3/8 inch balls are pressed in a lubricating oil with a load of 1 kgf, and the pressure is set to 0.03 m / sec.
When sliding at a relative velocity of 0.10 to 0.12, the friction coefficient of diamond-like carbon as a hard carbon film is 0.10 to 0.12.
The friction coefficient is the same between a steel material that is not treated with a film and a chromium nitride (CrN) ion plating treated film and a lubricating oil with the same surface roughness.

【０００９】一般に、エンジンオイルやトランスミッシ
ョンオイル等には耐摩耗性向上や摩擦特性向上を目的と
して種々の極圧添加剤が添加されており、これらの添加
剤は金属，主に鉄鋼製摺動部材の表面に吸着あるいは摺
動によって摺動部位表面に添加剤の反応生成物を生成す
ることによって、摩擦を低下させたり、金属同士の接触
を抑制し耐摩耗性を向上する効果を狙って添加してあ
る。Generally, various extreme pressure additives are added to engine oil and transmission oil for the purpose of improving abrasion resistance and friction characteristics, and these additives are made of metal, mainly steel sliding members. The reaction product of the additive is generated on the surface of the sliding part by adsorption or sliding on the surface of the steel, thereby reducing friction or suppressing the contact between metals to improve wear resistance. It is.

【００１０】ところが、このような添加剤を含む潤滑油
中にあってはプラズマＣＶＤ法等により処理された従来
の硬質炭素皮膜摺動部材では、表面が安定で、皮膜を施
さない金属表面に比べてオイル添加剤の吸着や添加剤反
応膜形成が生じにくく、添加剤の持つ性能を十分に引き
出せないことが判った。However, in a conventional hard carbon film sliding member treated by a plasma CVD method or the like in a lubricating oil containing such an additive, the surface is more stable than a metal surface having no coating. Thus, it was found that adsorption of an oil additive and formation of an additive reaction film were unlikely to occur, and the performance of the additive could not be sufficiently brought out.

【００１１】[0011]

【発明の目的】本発明は、これらの問題点に着目してな
されたものであり、炭素皮膜中の特定の金属含有量が５
〜７０ａｔ％である硬質炭素皮膜を処理した摺動部材と
することで、潤滑油中でもその固体潤滑性が有効に働
き、低摩擦で耐摩耗性に優れた摺動部材を提供すること
を目的としている。DISCLOSURE OF THE INVENTION The present invention has been made in view of these problems, and has a specific metal content of 5% in a carbon film.
The purpose of the present invention is to provide a sliding member which has a solid lubricating effect even in lubricating oil, and has low friction and excellent abrasion resistance by forming a sliding member treated with a hard carbon film of up to 70 at%. I have.

【００１２】[0012]

【問題を解決するための手段】上記目的を達成するため
鋭意研究した結果、硬質炭素皮膜における特定の金属元
素含有量が５〜７０ａｔ％含む構成としたことにより、
潤滑油中での低摩擦性能を実現可能とした。Means for Solving the Problems As a result of intensive studies to achieve the above object, the hard carbon film was designed to contain a specific metal element content of 5 to 70 at%.
Low friction performance in lubricating oil has been realized.

【００１３】この潤滑油中での硬質炭素皮膜の摩擦特性
については報告がほとんど無く、不明な点が多かった訳
であるが、本発明では硬質炭素皮膜に含まれる特定金属
元素濃度の潤滑油中での摩擦特性に及ぼす影響について
明らかにし、潤滑油中で低摩擦が実現できる硬質炭素皮
膜の特定金属元素濃度を規定したものである。There are few reports on the frictional properties of the hard carbon film in this lubricating oil, and there are many unclear points. The purpose of this study is to clarify the effect on frictional characteristics of steel and to specify the specific metal element concentration of a hard carbon film capable of realizing low friction in lubricating oil.

【００１４】すなわち、本発明に係る硬質炭素皮膜摺動
部材は、請求項１に記載しているように、潤滑油中で使
用される硬質炭素皮膜摺動部材において、少なくとも表
面層に元素周期律表の第ＩＩｂ，ＩＩＩ，ＩＶ，Ｖａ，
ＶＩａ，ＶＩＩａおよびＶＩＩＩ族のうちから選ばれる
少なくとも１種の金属元素を５〜７０ａｔ％含むものと
したことを特徴としている。That is, in the hard carbon film sliding member according to the present invention, at least the surface layer of the hard carbon film sliding member used in a lubricating oil has element periodicity. IIb, III, IV, Va,
It is characterized in that it contains at least one metal element selected from the groups VIa, VIIa and VIII in an amount of 5 to 70 at%.

【００１５】そして、本発明に係る硬質炭素皮膜摺動部
材においては、請求項２に記載しているように、金属元
素の含有量が２５〜６０ａｔ％の範囲であるものとする
ことができる。Further, in the hard carbon film sliding member according to the present invention, as described in claim 2, the content of the metal element can be in the range of 25 to 60 at%.

【００１６】また、請求項３に記載のように、前記金属
元素がモリブデン（Ｍｏ），タングステン（Ｗ），ニオ
ブ（Ｎｂ），チタン（Ｔｉ）および鉄（Ｆｅ）のうちか
ら選ばれるものとすることができ、請求項４に記載のよ
うに、硬質炭素皮膜摺動部材を構成する硬質炭素皮膜が
スパッタリング，プラズマＣＶＤあるいはイオンプレー
ティングにより作製されたダイヤモンドライクカーボン
膜（アモルファスカーボン膜）であるものとすることが
できる。According to a third aspect of the present invention, the metal element is selected from molybdenum (Mo), tungsten (W), niobium (Nb), titanium (Ti) and iron (Fe). Wherein the hard carbon film constituting the hard carbon film sliding member is a diamond-like carbon film (amorphous carbon film) produced by sputtering, plasma CVD, or ion plating. It can be.

【００１７】さらにまた、請求項５に記載のように、硬
質炭素皮膜の厚さが０．５μｍ以上１０μｍ以下であ
り、表面粗さがＲａ０．１μｍ以下でかつ表面硬度がＨ
ｖ１０００以上であるものとすることができる。Further, as described in claim 5, the thickness of the hard carbon film is 0.5 μm or more and 10 μm or less, the surface roughness is Ra 0.1 μm or less, and the surface hardness is H.
v1000 or more.

【００１８】さらにまた、請求項６に記載のように、金
属元素の含有量が２５〜６０ａｔ％であり、硬質炭素皮
膜の厚さが０．５μｍ以上１０μｍ以下であり、表面粗
さがＲａ０．１μｍ以下でかつ表面硬度がＨｖ１０００
以上であり、金属元素がモリブデン（Ｍｏ）であって硬
質炭素皮膜摺動部材を構成する硬質炭素皮膜がイオンプ
レーティングにより作製されたダイヤモンドライクカー
ボン膜（アモルファスカーボン膜）であるものとするこ
とができる。Further, as described in claim 6, the content of the metal element is 25 to 60 at%, the thickness of the hard carbon film is 0.5 μm or more and 10 μm or less, and the surface roughness is Ra0. 1 μm or less and surface hardness of Hv1000
The metal element is molybdenum (Mo), and the hard carbon film constituting the hard carbon film sliding member is a diamond-like carbon film (amorphous carbon film) produced by ion plating. it can.

【００１９】本発明による硬質炭素皮膜摺動部材は、請
求項７に記載のように、内燃機関の動弁機構のアジャス
ティングシムあるいはバルブリフターに用いられるもの
とすることができる。The hard carbon film sliding member according to the present invention can be used for an adjusting shim or a valve lifter of a valve train of an internal combustion engine.

【００２０】さらにまた、本発明による硬質炭素皮膜摺
動部材は、請求項８に記載のように、鉱油および合成油
を基油とし、モリブデンジチオカーバメートをモリブデ
ン量として５０〜１０００ｐｐｍ，ジチオリン酸亜鉛を
リン量として０．０１〜０．２ｗｔ％含む潤滑油中で使
用されるものとしたり、請求項９に記載のように、鉱油
および合成油を基油とし、硫化油脂，ポリサルファイ
ド，硫化オレフィンなどのいおう（Ｓ）系添加剤を含
み、そのいおう（Ｓ）成分の含有量が０．２ｗｔ％以上
である潤滑油中で使用されるものとしたりすることがで
きる。Further, the hard carbon film sliding member according to the present invention is characterized in that mineral oil and synthetic oil are used as base oils, molybdenum dithiocarbamate is used in an amount of 50 to 1000 ppm in terms of molybdenum, and zinc dithiophosphate is used. It may be used in a lubricating oil containing 0.01 to 0.2 wt% as a phosphorus amount, or as described in claim 9, a mineral oil and a synthetic oil as a base oil, and a sulfided oil, polysulfide, sulfided olefin and the like. It can be used in a lubricating oil containing a sulfur (S) -based additive and having a sulfur (S) component content of 0.2 wt% or more.

【００２１】[0021]

【発明の作用】本発明に係る硬質炭素皮膜摺動部材は、
上記の構成としたことにより、極圧添加剤が表面に吸着
しやすくかつ反応生成物を表面に形成しやすくなり、潤
滑油中で低摩擦な硬質炭素皮膜摺動部材とすることが可
能になる。たとえば、省燃費を目的としてエンジンオイ
ルなどに使用されるような鉱油および合成油を基油と
し、モリブデンジチオカーバメートをモリブデン量とし
て５０〜１０００ｐｐｍ，ジチオリン酸亜鉛をリン量と
して０．０１〜０．２ｗｔ％を含む潤滑油中において
は、従来の硬質炭素皮膜表面には潤滑油中に極圧添加剤
として添加されているモリブデンジチオカーバメートお
よびジチオリン酸亜鉛の添加剤皮膜が形成されず、従来
の炭素皮膜を形成しない鋼製の摺動部材よりも摩擦係数
が高くなっていたが、特定の金属、すなわち、元素周期
律表の第ＩＩｂ，ＩＩＩ，ＩＶ，Ｖａ，ＶＩａ，ＶＩＩ
ａおよびＶＩＩＩ族のうちから選ばれる少なくとも１種
の金属元素を５〜７０ａｔ％炭素皮膜に含有させること
で潤滑油添加剤の皮膜が表面に形成され、低い摩擦係数
が得られることとなる。The hard carbon film sliding member according to the present invention comprises:
With the above configuration, the extreme-pressure additive is easily adsorbed on the surface and a reaction product is easily formed on the surface, and a hard carbon film sliding member having low friction in lubricating oil can be obtained. . For example, mineral oil and synthetic oil used for engine oil and the like for the purpose of fuel saving are used as base oils, molybdenum dithiocarbamate is used as molybdenum in an amount of 50 to 1000 ppm, and zinc dithiophosphate is used as phosphorus in an amount of 0.01 to 0.2 wt. % Of lubricating oil containing molybdenum dithiocarbamate and zinc dithiophosphate added as extreme pressure additives in the lubricating oil is not formed on the surface of the conventional hard carbon film. Has a higher coefficient of friction than a steel sliding member that does not form any of the metals, but specific metals, namely, IIb, III, IV, Va, VIa, VII of the periodic table of elements.
By including at least one metal element selected from the group a and group VIII in the carbon film at 5 to 70 at%, a film of the lubricant additive is formed on the surface, and a low coefficient of friction can be obtained.

【００２２】そして、硬質炭素皮膜表面の特定金属含有
濃度が５ａｔ％未満であるとその低摩擦効果が得られ
ず、７０ａｔ％超過となると高面圧下での耐摩耗性が不
足するようになるため、７０ａｔ％を上限とした。If the specific metal content on the surface of the hard carbon film is less than 5 at%, the low friction effect cannot be obtained, and if it exceeds 70 at%, the abrasion resistance under high surface pressure becomes insufficient. , 70 at% as the upper limit.

【００２３】さらに好ましくは、特定金属元素含有量を
２５〜６０ａｔ％の範囲とすることが耐摩耗性，平滑性
を損なうことなく、潤滑油中での低摩擦特性が得られる
こととなる。また、炭素皮膜に添加する金属元素は、元
素周期律表第ＩＩｂ，ＩＩＩ，ＩＶ，Ｖａ，ＶＩａ，Ｖ
ＩＩａおよびＶＩＩＩ族のうち、添加剤の反応皮膜形成
を考慮した場合に、モリブデン（Ｍｏ），タングステン
（Ｗ），ニオブ（Ｎｂ），チタン（Ｔｉ）および鉄（Ｆ
ｅ）のうちから選ばれるものとすることが好ましい。More preferably, when the content of the specific metal element is in the range of 25 to 60 at%, low friction characteristics in lubricating oil can be obtained without impairing wear resistance and smoothness. The metal elements to be added to the carbon film are listed in the Periodic Table of the Elements IIb, III, IV, Va, VIa, V
Of the groups IIa and VIII, when considering the formation of a reaction film of the additive, molybdenum (Mo), tungsten (W), niobium (Nb), titanium (Ti) and iron (F)
Preferably, it is selected from e).

【００２４】炭素皮膜の表面粗さについては、低摩擦特
性と相手攻撃性を考慮して、Ｒａ０．１μｍ以下とする
ことが好ましく、表面硬度は耐摩耗性が確保できるＨｖ
１０００以上とすることが好ましい。また、表面皮膜の
膜厚については、０．５μｍ未満であると密着強度が不
足する傾向となり、１０μｍ超過となると膜内の残留応
力が大きくなり、自然に剥離してしまう可能性があるた
め、膜厚は０．５〜１０μｍの範囲とすることが好まし
い。The surface roughness of the carbon film is preferably set to Ra 0.1 μm or less in consideration of low friction characteristics and aggressiveness against a partner, and the surface hardness is Hv at which abrasion resistance can be secured.
It is preferred to be 1000 or more. Also, regarding the thickness of the surface film, if it is less than 0.5 μm, the adhesive strength tends to be insufficient, and if it exceeds 10 μm, the residual stress in the film increases, and there is a possibility that the film will be spontaneously peeled off. The thickness is preferably in the range of 0.5 to 10 μm.

【００２５】[0025]

【発明の効果】本発明による硬質炭素皮膜摺動部材によ
れば、潤滑油中で使用される硬質炭素皮膜摺動部材にお
いて、少なくとも表面層に元素周期律表の第ＩＩｂ，Ｉ
ＩＩ，ＩＶ，Ｖａ，ＶＩａ，ＶＩＩａおよびＶＩＩＩ族
のうちから選ばれる少なくとも１種の金属元素を５〜７
０ａｔ％含むものとしたから、極圧添加剤が裏面に吸着
しやすくかつ反応生成物を表面に形成しやすくなり、潤
滑油中で低摩擦な硬質炭素皮膜摺動部材とすることが可
能になるという著しく優れた効果がもたらされる。According to the hard carbon film sliding member according to the present invention, in a hard carbon film sliding member used in lubricating oil, at least the surface layer has at least a surface layer IIb, I of the periodic table of elements.
At least one metal element selected from the group consisting of groups II, IV, Va, VIa, VIIa and VIII;
Since it is contained at 0 at%, the extreme pressure additive is easily adsorbed on the back surface and the reaction product is easily formed on the surface, so that a hard carbon film sliding member having low friction in lubricating oil can be obtained. This is a remarkably excellent effect.

【００２６】そして、請求項２に記載しているように、
金属元素の含有量が２５〜６０ａｔ％の範囲であるもの
とすることによって、耐摩耗性，平滑性を損うことな
く、潤滑油中での低摩擦特性を得ることが可能になると
いう著しく優れた効果がもたらされる。And, as described in claim 2,
By setting the content of the metal element in the range of 25 to 60 at%, it is extremely excellent that low friction characteristics in a lubricating oil can be obtained without impairing wear resistance and smoothness. The effect is brought about.

【００２７】そしてまた、請求項３に記載しているよう
に、前記金属元素がモリブデン（Ｍｏ），タングステン
（Ｗ），ニオブ（Ｎｂ），チタン（Ｔｉ）および鉄（Ｆ
ｅ）のうちから選ばれるものとすることによって、添加
剤の反応皮膜形成を考慮した場合に有効なものになるこ
とがあるという著しく優れた効果がもたらされる。Further, as described in claim 3, the metal elements are molybdenum (Mo), tungsten (W), niobium (Nb), titanium (Ti) and iron (F).
By being selected from e), a remarkably excellent effect is brought about which may be effective in consideration of the formation of a reaction film of the additive.

【００２８】さらにまた、請求項４に記載しているよう
に、硬質炭素皮膜摺動部材を構成する硬質炭素皮膜がス
パッタリング，プラズマＣＶＤあるいはイオンプレーテ
ィングにより作製されたダイヤモンドライクカーボン膜
（アモルファスカーボン膜）であるものとすることによ
って、高硬度で、表面が平滑で、耐摩耗性に優れ、それ
自体のもつ固体潤滑性能により低摩擦係数で優れた低摩
擦性能を有する硬質炭素皮膜とすることが可能であると
いう著しく優れた効果がもたらされる。Further, as described in claim 4, the hard carbon film constituting the hard carbon film sliding member is a diamond-like carbon film (amorphous carbon film) formed by sputtering, plasma CVD or ion plating. ) To provide a hard carbon film having high hardness, smooth surface, excellent wear resistance, and low friction coefficient and excellent low friction performance due to its own solid lubrication performance. A remarkably excellent effect is achieved.

【００２９】さらにまた、請求項５に記載のように、硬
質炭素皮膜の厚さが０．５μｍ以上１０μｍ以下である
ものとすることによって、膜厚が小さいことによる密着
強度の低下を防ぐと共に膜厚が大きいことによる膜内の
残留応力の増大を防ぐことが可能となり、また、表面粗
さがＲａ０．１μｍ以下でかつ表面硬度がＨｖ１０００
以上であるものとすることによって、表面粗さが大きい
ことによる低摩擦特性の劣化と相手攻撃性の増大を防ぐ
ことが可能となり、表面硬度をＨｖ１０００以上とする
ことで良好な耐摩耗性が確保できるようになるという著
しく優れた効果がもたらされる。Further, as described in claim 5, by setting the thickness of the hard carbon film to be 0.5 μm or more and 10 μm or less, it is possible to prevent a decrease in adhesion strength due to a small film thickness and to prevent the film from becoming thin. An increase in residual stress in the film due to a large thickness can be prevented, and a surface roughness Ra of 0.1 μm or less and a surface hardness of Hv 1000
With the above, it is possible to prevent the deterioration of the low friction property and the increase of the aggressiveness of the opponent due to the large surface roughness, and to secure the good wear resistance by setting the surface hardness to Hv1000 or more. A remarkably excellent effect of being able to do so.

【００３０】さらにまた、請求項６に記載のように、金
属元素の含有量が２５〜６０ａｔ％であり、硬質炭素皮
膜の厚さが０．５μｍ以上１０μｍ以下であり、表面粗
さがＲａ０．１μｍ以下でかつ表面硬度がＨｖ１０００
以上であり、金属元素がモリブデン（Ｍｏ）であって硬
質炭素皮膜摺動部材を構成する硬質炭素皮膜がイオンプ
レーティングにより作製されたダイヤモンドライクカー
ボン膜（アモルファスカーボン膜）であるものとするこ
とによって、潤滑剤中で低摩擦であって摺動特性により
一層優れた摺動部材を提供することが可能であるという
著大なる効果がもたらされる。Further, as described in claim 6, the content of the metal element is 25 to 60 at%, the thickness of the hard carbon film is 0.5 μm or more and 10 μm or less, and the surface roughness is Ra0. 1 μm or less and surface hardness of Hv1000
As described above, the metal element is molybdenum (Mo), and the hard carbon film constituting the hard carbon film sliding member is a diamond-like carbon film (amorphous carbon film) produced by ion plating. In addition, a remarkable effect that a sliding member having low friction in a lubricant and having more excellent sliding characteristics can be provided can be provided.

【００３１】さらにまた、請求項７に記載のように、内
燃機関の動弁機構のアジャスティングシムあるいはバル
ブリフターに用いることによって、内燃機関の動弁特性
をより一層良好なものにすることが可能になるという著
しく優れた効果がもたらされる。Furthermore, by using the adjusting shim or the valve lifter of the valve operating mechanism of the internal combustion engine as described in claim 7, the valve operating characteristics of the internal combustion engine can be further improved. Significantly improved effect.

【００３２】さらにまた、請求項８に記載のように、鉱
油および合成油を基油とし、モリブデンジチオカーバメ
ートをモリブデン量として５０〜１０００ｐｐｍ，ジチ
オリン酸亜鉛をリン量として０．０１〜０．２ｗｔ％含
む潤滑油中で使用されるようになすことによって、潤滑
油添加剤の皮膜が表面に形成され、低い摩擦係数を得る
ことが可能になるという著しく優れた効果がもたらされ
る。Further, as described in claim 8, a mineral oil and a synthetic oil are used as base oils, molybdenum dithiocarbamate in an amount of 50 to 1000 ppm in terms of molybdenum, and zinc dithiophosphate in an amount of 0.01 to 0.2 wt% in terms of phosphorus. By being used in a lubricating oil containing lubricating oil, a remarkable effect is brought about in that a film of the lubricating oil additive is formed on the surface and a low coefficient of friction can be obtained.

【００３３】さらにまた、請求項９に記載のように、鉱
油および合成油を基油とし、硫化油脂，ポリサルファイ
ド，硫化オレフィンなどのいおう（Ｓ）系添加剤を含
み、そのいおう（Ｓ）成分の含有量が０．２ｗｔ％以上
である潤滑油中で使用されるようになすことによって、
潤滑油中での十分良好な低摩擦性能を実現することが可
能になるという著しく優れた効果がもたらされる。Further, as set forth in claim 9, a mineral oil and a synthetic oil are used as base oils, and sulfur (S) based additives such as sulfurized fats and oils, polysulfide, and sulfurized olefins are contained. By being used in a lubricating oil having a content of 0.2 wt% or more,
A remarkably excellent effect is achieved in that it is possible to realize sufficiently good low friction performance in lubricating oil.

【００３４】[0034]

【実施例】以下、本発明を実施例により詳細に説明する
が、本発明は以下に示す実施例に限定されないことはい
うまでもない。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but it goes without saying that the present invention is not limited to the following Examples.

【００３５】（実施例１〜７）図１に示すような直径３
０ｍｍ，厚み４ｍｍの円板基材１１の上に硬質炭素皮膜
１２をコーティングした試験片１０により、摩擦試験を
行った。このときの試験片１０は表１に示すような仕様
で円板基材１１の上に硬質炭素皮膜１２を作製したもの
とした。(Embodiments 1 to 7) As shown in FIG.
A friction test was performed using a test piece 10 in which a hard carbon film 12 was coated on a disk substrate 11 having a thickness of 0 mm and a thickness of 4 mm. At this time, the test piece 10 had a hard carbon film 12 formed on a disk base material 11 according to the specifications shown in Table 1.

【００３６】実施例１は浸炭鋼（ＪＩＳ ＳＣＭ４１
５）よりなる基材１１の表面をＲａ０．０４μｍの超仕
上げ加工した後、炭化水素ガスを用いたプラズマＣＶＤ
法により硬質炭素皮膜をコーティングしながら、Ｍｏを
ターゲット材料としたスパッタリング法を同一の真空容
器内で行い炭素皮膜表面のＭｏ濃度が２７ａｔ％となる
ようにＭｏ元素を炭素皮膜中に添加した。成膜後仕上げ
加工無しで皮膜表面はＲａ０．０９μｍであった。In Example 1, a case of carburized steel (JIS SCM41) was used.
5) The surface of the base material 11 is super-finished with Ra of 0.04 μm, and is then subjected to plasma CVD using a hydrocarbon gas.
While coating the hard carbon film by the method, a sputtering method using Mo as a target material was performed in the same vacuum vessel, and Mo element was added to the carbon film so that the Mo concentration on the surface of the carbon film became 27 at%. After the film formation, the surface of the film was Ra 0.09 μm without finishing.

【００３７】実施例２は基材１１の表面をＲａ０．０４
μｍに超仕上げ加工した後、プラズマＣＶＤ装置で炭化
水素ガスを用いてダイヤモンドライクカーボン（ＤＬ
Ｃ）皮膜１２を基材１１の上に成膜した後さらにＷをタ
ーゲット材料としたスパッタリング法によりＷをコーテ
ィングし、これを交互に繰り返して積層膜とすることで
硬質炭素皮膜表面のＷ濃度が４８ａｔ％となるようにＷ
元素を炭素皮膜中に添加した。In Example 2, the surface of the substrate 11 was treated with Ra 0.04
μm, and then diamond-like carbon (DL) using hydrocarbon gas with a plasma CVD device.
C) After the film 12 is formed on the substrate 11, W is further coated by a sputtering method using W as a target material, and this is alternately repeated to form a laminated film. W to be 48at%
Elements were added into the carbon coating.

【００３８】実施例３〜６は実施例１のＭｏターゲット
材料の変わりに、それぞれの添加金属のＦｅ，Ｔｉ，Ｃ
ｒ，Ｗをターゲット材料として使用し、実施例１と同様
の方法で炭素皮膜表面の添加金属濃度が表１の値となる
ように金属元素を炭素皮膜中に添加した。それぞれの硬
質炭素皮膜の濃度は、実施例３でＦｅ３０ａｔ％、実施
例４でＴｉ２５ａｔ％、実施例５でＣｒ３０ａｔ％、実
施例６でＷ１０ａｔ％であった。成膜後仕上げ加工無し
でそれぞれの皮膜表面粗さはＲａ０．０７〜０．０８μ
ｍであった。In Examples 3 to 6, instead of the Mo target material of Example 1, Fe, Ti, C
Using r and W as target materials, a metal element was added to the carbon film in the same manner as in Example 1 so that the concentration of the added metal on the surface of the carbon film became the value shown in Table 1. The concentration of each hard carbon film was 30 at% of Fe in Example 3, 25 at% of Ti in Example 4, 30 at% of Cr in Example 5, and 10 at% of W in Example 6. The surface roughness of each film is Ra 0.07-0.08μ without finishing after film formation.
m.

【００３９】実施例７は浸炭鋼（ＪＩＳ ＳＣＭ４１
５）よりなる基材１１の表面をＲａ０．０４μｍの超仕
上げ加工した後、蒸発源としてグラファイトとモリブデ
ン（Ｍｏ）を用いたイオンプレーティング法により硬質
炭素皮膜をコーティングしながら、Ｍｏのコーティング
を同一の真空容器内で行い炭素皮膜表面のＭｏ濃度が４
０ａｔ％となるようにＭｏ元素を炭素皮膜中に添加し
た。成膜後仕上げ加工無しでそれぞれの皮膜表面粗さは
Ｒａ０．０９μｍであった。In Example 7, carburized steel (JIS SCM41) was used.
After the surface of the base material 11 made of 5) is super-finished with Ra of 0.04 μm, the coating of Mo is made the same while coating the hard carbon film by an ion plating method using graphite and molybdenum (Mo) as evaporation sources. In a vacuum vessel, the Mo concentration on the carbon film surface was 4
Mo element was added to the carbon film so as to be 0 at%. The surface roughness of each film was Ra 0.09 μm without finishing after film formation.

【００４０】（比較例１〜５）表１に示すような比較例
の摺動部材を製作したうち、比較例１は浸炭鋼（ＪＩＳ
ＳＣＭ４１５）よりなる基材１１の表面をＲａ０．２
４μｍに研削加工した摺動部材、比較例２は比較例１の
摺動部材に更にイオンプレーティング法により２．０μ
ｍの膜厚を有する硬度Ｈｖ１５００の窒化チタン（Ｔｉ
Ｎ）皮膜のコーティングを施した摺動部材、比較例３は
浸炭鋼（ＪＩＳ ＳＣＭ４１５）よりなる基材１１の表
面をＲａ０．０４μｍの超仕上げ加工した後、プラズマ
ＣＶＤ装置で炭化水素ガスを用いてダイヤモンドライク
カーボン（ＤＬＣ）皮膜１２を基材１１の上に成膜した
摺動部材である。(Comparative Examples 1 to 5) Among the sliding members of Comparative Examples shown in Table 1, Comparative Example 1 was made of carburized steel (JIS).
The surface of the substrate 11 made of SCM415) is Ra0.2
The sliding member ground to 4 μm, Comparative Example 2 was further added to the sliding member of Comparative Example 1 by 2.0 μm by the ion plating method.
m and a hardness Hv1500 of titanium nitride (Ti
N) A sliding member coated with a film. In Comparative Example 3, the surface of the base material 11 made of carburized steel (JIS SCM415) was super-finished with a Ra of 0.04 μm, and then a hydrocarbon gas was used in a plasma CVD apparatus. The sliding member has a diamond-like carbon (DLC) film 12 formed on a substrate 11.

【００４１】さらに、比較例４は実施例６と同様の方法
で表面のＷ濃度が２ａｔ％となるようにＷ元素を硬質炭
素皮膜に添加した摺動部材、比較例５は実施例６と同様
の方法で表面のＷ濃度が８０ａｔ％となるようにＷ元素
を硬質炭素皮膜に添加した摺動部材である。 （摩擦試験例）摩擦試験装置としては図２（ａ）に示す
ようなピンオンディスクタイプの摩耗試験機２０を用い
て摩擦係数を計測した。この装置は回転軸２１に回転自
在に支持されたワークテーブル２２が回転自在に配置さ
れ、このワークテーブル２２に試験片摺動部材２３を設
置し、この試験片摺動部材２３の上面側に外径φ５ｍ
ｍ，長さ５ｍｍのころ軸受用ＳＵＪ２ローラをピンとし
て用いて、ピン２４を図２（ｂ）に示すように３個配置
し、スプリング２５によって荷重Ｐ：１．０ｋｇで押し
付けるように構成されたものである。このとき、ピン２
４はホルダー２４Ｈに回転できないようにそれぞれ固定
されている。そして、回転軸２１がモータ２６に連結さ
れてボールピン２４に対して相対滑り速度０．０１〜
１．０ｍ／ｓｅｃで回転駆動され、ピン２４と試験片摺
動部材２３との間で発生する摩擦力に応じたトルクをロ
ードセル２７で計測し、摩擦係数を算出するものとして
いる。また、試験片摺動部材２３が潤滑油２８Ｌ中に浸
漬されるように、油浴槽２８が設置され、図示しない油
温コントロールユニットにより油温が８０℃となるよう
に設定されているものとした。Further, Comparative Example 4 is a sliding member in which W is added to the hard carbon film so that the W concentration on the surface becomes 2 at% in the same manner as in Example 6, and Comparative Example 5 is the same as Example 6. This is a sliding member in which W element is added to the hard carbon film so that the W concentration on the surface becomes 80 at% by the method described in (1). (Example of friction test) As a friction test apparatus, a friction coefficient was measured using a pin-on-disk type wear tester 20 as shown in FIG. In this apparatus, a work table 22 rotatably supported by a rotating shaft 21 is rotatably arranged, and a test piece sliding member 23 is installed on the work table 22. Diameter φ5m
As shown in FIG. 2B, three pins 24 are arranged using a SUJ2 roller for roller bearings having a length of 5 mm and a length of 5 mm, and are pressed by a spring 25 with a load P: 1.0 kg. Things. At this time, pin 2
4 are fixed to the holder 24H so that they cannot rotate. Then, the rotating shaft 21 is connected to the motor 26 and the relative sliding speed with respect to the ball pin 24 is 0.01 to 0.01.
The load cell 27 is rotated at 1.0 m / sec, measures a torque corresponding to a frictional force generated between the pin 24 and the test piece sliding member 23, and calculates a friction coefficient. The oil bath 28 was installed so that the test piece sliding member 23 was immersed in the lubricating oil 28L, and the oil temperature was set to 80 ° C. by an oil temperature control unit (not shown). .

【００４２】表１に各実施例および比較例の摺動部材を
摩擦試験機２０の試験片摺動部材２３として配置し、潤
滑油中で摩擦係数を測定した結果を示す。Table 1 shows the results of measuring the friction coefficient in lubricating oil by arranging the sliding members of Examples and Comparative Examples as the test piece sliding member 23 of the friction tester 20.

【００４３】試験条件は、３個のピン２４への負荷荷重
１５ｋｇｆ（面圧０．２３ＧＰａ）、滑り速度０．０３
〜１．０ｍ／ｓｅｃ（３０〜１０００ｒｐｍ）で行っ
た。潤滑油は、通常のエンジンオイル，鉱油を基油とし
モリブデンジチオカーバメートをモリブデン量として５
００ｐｐｍ，ジチオリン酸亜鉛をリン量として０．１２
ｗｔ％を含む摩擦低減を目的としたエンジンオイル、お
よび鉱油を基油とし、ポリサルファイド，硫化オレフィ
ンのいおう（Ｓ）系添加剤を含み、潤滑油中のいおう
（Ｓ）含有量が０．５ｗｔ％であるＳ系添加剤潤滑油を
使用した。The test conditions were as follows: the load applied to the three pins 24 was 15 kgf (surface pressure: 0.23 GPa), and the sliding speed was 0.03.
１．０1.0 m / sec (30 to 1000 rpm). The lubricating oil is usually engine oil, mineral oil as a base oil and molybdenum dithiocarbamate in a molybdenum amount of 5%.
00 ppm, zinc dithiophosphate 0.12
engine oil for the purpose of friction reduction, including mineral oil, and mineral oil as base oils, containing sulfur (S) additives of polysulfide and sulfurized olefin, and having sulfur (S) content of 0.5 wt% in lubricating oil Was used.

【００４４】[0044]

【表１】 [Table 1]

【００４５】表１および図３，図４，図５に示すすべり
速度０．５ｍ／ｓ（５００ｒｐｍ）での摩擦係数の計測
結果から判るように、特定の金属を添加した実施例１〜
７の硬質炭素皮膜は通常のエンジンオイル中では比較例
１〜５のいずれよりも低摩擦であり、添加剤反応皮膜が
形成されることによる効果と考えられた。また、鉱油を
基油としモリブデンジチオカーバメートをモリブデン量
として５００ｐｐｍ，ジチオリン酸亜鉛をリン量として
０．１２ｗｔ％を含むエンジンオイル中の試験では、金
属を添加しない比較例３の硬質炭素皮膜をコーティング
した摺動部材に比べて、金属を含有した実施例１〜７の
硬質炭素皮膜摺動部材は低い摩擦係数を示し、実施例２
および７の硬質炭素皮膜摺動部材は比較例１の摩擦係数
と同等であり、硬質炭素皮膜へ金属を含有させることに
よって、鋼製摺動部材と同等の表面添加剤皮膜反応が生
じるようになったものと考えられた。As can be seen from the measurement results of the coefficient of friction at a sliding speed of 0.5 m / s (500 rpm) shown in Table 1 and FIGS.
The hard carbon film of No. 7 had lower friction in normal engine oil than any of Comparative Examples 1 to 5, and was considered to be an effect due to the formation of the additive reaction film. In a test in an engine oil containing a mineral oil as a base oil, molybdenum dithiocarbamate as a molybdenum amount of 500 ppm, and zinc dithiophosphate as a phosphorus amount of 0.12 wt%, the hard carbon film of Comparative Example 3 without metal was coated. As compared with the sliding member, the hard carbon film sliding members of Examples 1 to 7 containing a metal showed a lower coefficient of friction.
The hard carbon film sliding members of Nos. 7 and 7 have the same coefficient of friction as Comparative Example 1, and the addition of a metal to the hard carbon film causes a surface additive film reaction equivalent to that of a steel sliding member. It was thought that it was.

【００４６】これに対して、金属を含有しない比較例３
や金属添加量が５ａｔ％未満の硬質炭素皮膜摺動部材や
比較例２の摺動部材にあっては、相手材ピンには添加剤
皮膜が生成されるものの、自身の表面には皮膜が生成さ
れないため、比較例１や実施例のような摩擦の低減効果
は得られないことが判った。On the other hand, Comparative Example 3 containing no metal
And a hard carbon film sliding member having a metal addition amount of less than 5 at% and a sliding member of Comparative Example 2, an additive film is formed on the mating pin, but a film is formed on its own surface. Therefore, it was found that the effect of reducing friction as in Comparative Example 1 and Example was not obtained.

【００４７】また、実施例２〜７と比較例３，４の比較
から、鉱油を基油としポリサルファイド，硫化オレフィ
ンのいおう（Ｓ）系添加剤を含み、潤滑油中のいおう
（Ｓ）含有量が０．５ｗｔ％であるＳ系添加剤潤滑油に
あっても同様のことがいえる。From the comparison between Examples 2 to 7 and Comparative Examples 3 and 4, the sulfur (S) content of the lubricating oil was determined using mineral oil as the base oil, containing sulfur (S) additives of polysulfide and sulfurized olefin. The same can be said for the S-based additive lubricating oil having a content of 0.5 wt%.

【００４８】（実機試験例）実施例２および７の硬質炭
素皮膜摺動部材を図６に示すような内燃機関の動弁機構
のアジャスティングシム６０に用いた場合のカム一つ当
たりの摩擦損失トルクを計測した。このとき、トルク計
測は図示していないカムシャフト軸５２に取り付けられ
たトルク計で計測した。(Test Example of Actual Machine) Friction loss per cam when the hard carbon film sliding members of Examples 2 and 7 are used for an adjusting shim 60 of a valve mechanism of an internal combustion engine as shown in FIG. The torque was measured. At this time, the torque was measured by a torque meter attached to the cam shaft 52 (not shown).

【００４９】図６に示す内燃機関の動弁機構において、
吸気バルブ又は排気バルブ５３はバルブガイド５４に挿
通され、バルブ５３の軸端の上方にバルブリフター５５
が設置されている。また、シリンダヘッド５６とバルブ
リフター５５の間にはバルブスプリング５７がリテーナ
５８とコッタ５９によりバルブ５３に固定され、バルブ
５３を閉じる方向にスプリング５７による荷重を負荷し
ている。さらにまた、バルブリフター５５の上面には図
に示すようにアジャスティングシム６０が嵌合されてお
り、カム５１とのクリアランスが０．３ｍｍ程度となる
ようにアジャスティングシム６０の厚さにより調整され
ている。さらに、カムシャフト軸５２は図示していない
クランクシャフトの駆動によりタイミングベルトを介し
て駆動される。そして、カムシャフト軸５２が駆動する
ことによりカム５１が回転し、アジャスティングシム６
０と摺接し、バルブ５３を往復運動させる機構となって
いる。このときの試験条件は、カム軸回転数３００ｒｐ
ｍ（アイドリング時相当）、スプリングＭａｘ荷重５０
ｋｇｆ、エンジン油温８０℃で、アジャスティングシム
６０と摺動する相手カム５１の表面粗さは超仕上げ加工
を施し、Ｒａ０．０５μｍに仕上げられているものとし
ている。In the valve mechanism of the internal combustion engine shown in FIG.
The intake valve or exhaust valve 53 is inserted into a valve guide 54, and a valve lifter 55 is provided above an axial end of the valve 53.
Is installed. A valve spring 57 is fixed to the valve 53 between the cylinder head 56 and the valve lifter 55 by a retainer 58 and a cotter 59, and applies a load by the spring 57 in a direction to close the valve 53. Further, an adjusting shim 60 is fitted on the upper surface of the valve lifter 55 as shown in the figure, and is adjusted by the thickness of the adjusting shim 60 so that the clearance with the cam 51 becomes about 0.3 mm. ing. Further, the camshaft shaft 52 is driven via a timing belt by driving a crankshaft (not shown). When the camshaft shaft 52 is driven, the cam 51 rotates, and the adjusting shim 6
The valve 53 slides and makes the valve 53 reciprocate. The test condition at this time is that the camshaft rotation speed is 300 rpm
m (equivalent to idling), Spring Max load 50
The surface roughness of the mating cam 51 sliding with the adjusting shim 60 at kgf and the engine oil temperature of 80 ° C. is super-finished, and is finished to Ra 0.05 μm.

【００５０】比較のために、従来使用されている比較例
１および硬質炭素皮膜コーティングした比較例３の摺動
部材を同様にアジャスティングシム６０に用いた場合の
損失トルクも同じ条件にて計測した。計測した結果を図
５に示す。このとき、エンジンオイルは従来のエンジン
オイル５Ｗ−３０ＳＪおよび５Ｗ−３０相当粘度のモリ
ブデンジチオカーバメートをモリブデン量として５００
ｐｐｍ、ジチオリン酸亜鉛をリン量として０．１２ｗｔ
％を含むエンジンオイルを使用した。For comparison, the torque loss in the case where the conventional sliding member of Comparative Example 1 and Comparative Example 3 coated with a hard carbon film were used for the adjusting shim 60 was also measured under the same conditions. . FIG. 5 shows the measured results. At this time, as the engine oil, molybdenum dithiocarbamate having a viscosity equivalent to that of the conventional engine oil 5W-30SJ or 5W-30 was used as a molybdenum amount of 500.
ppm, zinc dithiophosphate 0.12wt
% Engine oil was used.

【００５１】図７に示す損失トルクの計測結果から判る
ように、ピンディスク摩擦試験と同様に、比較例に比べ
て実施例のアジャスティングシムは摩擦損失トルクが小
さく、低摩擦性能に優れていることが認められた。そし
て特に、イオンプレーティング法を用いた実施例７はど
ちらのオイルにおいても低い摩擦トルクとなった。As can be seen from the measurement result of the loss torque shown in FIG. 7, the adjusting shim of the example has a small friction loss torque and is excellent in the low friction performance as compared with the comparative example, similarly to the pin disk friction test. It was recognized that. In particular, in Example 7 using the ion plating method, the friction torque was low in both oils.

【図面の簡単な説明】[Brief description of the drawings]

【図１】円板基材の上に硬質炭素皮膜をコーティングし
た試験片の斜面説明図である。FIG. 1 is an explanatory view of a slope of a test piece in which a hard carbon film is coated on a disk substrate.

【図２】本発明の評価に使用した摩擦試験機の断面説明
図である。FIG. 2 is an explanatory sectional view of a friction tester used for evaluation of the present invention.

【図３】摩擦試験機によるエンジンオイル中での摩擦係
数計測結果を示すグラフである。FIG. 3 is a graph showing a measurement result of a friction coefficient in engine oil by a friction tester.

【図４】摩擦試験機によるＭｏジチオカーバメート添加
剤油中での摩擦係数計測結果を示すグラフである。FIG. 4 is a graph showing the results of measurement of the coefficient of friction in Mo dithiocarbamate additive oil using a friction tester.

【図５】摩擦試験機によるいおう添加剤油中での摩擦係
数試験結果を示すグラフである。FIG. 5 is a graph showing the results of a friction coefficient test in a sulfur additive oil by a friction tester.

【図６】内燃機関の動弁装置の断面説明図である。FIG. 6 is an explanatory sectional view of a valve gear of the internal combustion engine.

【図７】摩擦損失トルク計測結果を示すグラフである。FIG. 7 is a graph showing friction loss torque measurement results.

【符号の説明】[Explanation of symbols]

１０ 試験片 １１ 円板基材 １２ 硬質炭素皮膜 Reference Signs List 10 Test piece 11 Disc base material 12 Hard carbon coating

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ１０Ｍ 135/20 Ｃ１０Ｍ 135/20 137/10 137/10 Ａ Ｃ２３Ｃ 14/06 Ｃ２３Ｃ 14/06 Ｆ 16/27 16/27 Ｆ０１Ｌ 1/14 Ｆ０１Ｌ 1/14 Ｂ 1/20 1/20 Ａ Ｆ１６Ｃ 33/12 Ｆ１６Ｃ 33/12 Ａ 33/24 33/24 Ｚ // Ｃ１０Ｎ 10:04 Ｃ１０Ｎ 10:04 10:06 10:06 10:08 10:08 10:10 10:10 10:12 10:12 10:14 10:14 10:16 10:16 30:06 30:06 40:02 40:02 40:04 40:04 40:25 40:25 (72)発明者 馬 渕 豊 神奈川県横浜市神奈川区宝町２番地 日産 自動車株式会社内 Ｆターム(参考） 3G016 AA06 AA19 BA47 BB04 BB05 BB06 BB40 DA12 EA02 EA07 EA11 EA24 FA21 GA02 3J011 AA10 DA01 DA02 JA02 MA02 MA22 QA03 QA04 RA03 SB01 SB02 SB13 SB14 SE02 4H104 AA04A AA08C BG02C BG04C BG10C BG12C BH07C DA02A EB02 FA02 FA03 FA04 FA05 FA06 FA07 FA08 LA03 PA01 PA03 PA41 4K029 AA02 AA24 BA01 BA07 BA09 BA11 BA17 BA34 BB02 BD04 CA03 CA05 FA03 4K030 BA27 BA28 BB12 CA02 CA17 DA02 FA01 KA30 LA23 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C10M 135/20 C10M 135/20 137/10 137/10 A C23C 14/06 C23C 14/06 F 16/27 16/27 F01L 1/14 F01L 1/14 B 1/20 1/20 A F16C 33/12 F16C 33/12 A 33/24 33/24 Z // C10N 10:04 C10N 10:04 10:06 10: 06 10:08 10:08 10:10 10:10 10:12 10:12 10:14 10:14 10:16 10:16 30:06 30:06 40:02 40:02 40:04 40:04 40 : 25 40:25 (72) Inventor: Yutaka Mabuchi Yutaka 2nd, Takaracho, Kanagawa-ku, Yokohama-shi, Kanagawa F-term (reference) in Nissan Motor Co., Ltd. DA02 JA02 MA02 MA22 QA03 QA04 RA03 SB01 SB02 SB13 SB14 SE02 4H104 AA04A AA08C BG02C BG04C BG10C BG12C BH07C DA02A EB02 FA02 FA03 FA04 FA0 5 FA06 FA07 FA08 LA03 PA01 PA03 PA41 4K029 AA02 AA24 BA01 BA07 BA09 BA11 BA17 BA34 BB02 BD04 CA03 CA05 FA03 4K030 BA27 BA28 BB12 CA02 CA17 DA02 FA01 KA30 LA23

Claims (9)

【特許請求の範囲】[Claims] 【請求項１】 潤滑油中で使用される硬質炭素皮膜摺動
部材において、少なくとも表面層に元素周期律表の第Ｉ
Ｉｂ，ＩＩＩ，ＩＶ，Ｖａ，ＶＩａ，ＶＩＩａおよびＶ
ＩＩＩ族のうちから選ばれる少なくとも１種の金属元素
を５〜７０ａｔ％含むことを特徴とする硬質炭素皮膜摺
動部材。1. A hard carbon film sliding member used in a lubricating oil, wherein at least a surface layer of the sliding member has the I-th element of the periodic table.
Ib, III, IV, Va, VIa, VIIa and V
A hard carbon film sliding member comprising 5 to 70 at% of at least one metal element selected from Group III. 【請求項２】 金属元素の含有量が２５〜６０ａｔ％の
範囲であることを特徴とする請求項１に記載の硬質炭素
皮膜摺動部材。2. The hard carbon film sliding member according to claim 1, wherein the content of the metal element is in the range of 25 to 60 at%. 【請求項３】 金属元素がモリブデン（Ｍｏ），タング
ステン（Ｗ），ニオブ（Ｎｂ），チタン（Ｔｉ）および
鉄（Ｆｅ）のうちから選ばれることを特徴とする請求項
１または２に記載の硬質炭素皮膜摺動部材。3. The method according to claim 1, wherein the metal element is selected from molybdenum (Mo), tungsten (W), niobium (Nb), titanium (Ti) and iron (Fe). Hard carbon film sliding member. 【請求項４】 硬質炭素皮膜摺動部材を構成する硬質炭
素皮膜がスパッタリング，プラズマＣＶＤあるいはイオ
ンプレーティングにより作製されたダイヤモンドライク
カーボン膜（アモルファスカーボン膜）であることを特
徴とする請求項１ないし３のいずれかに記載の硬質炭素
皮膜摺動部材。4. The hard carbon film forming the hard carbon film sliding member is a diamond-like carbon film (amorphous carbon film) produced by sputtering, plasma CVD or ion plating. 4. The sliding member for a hard carbon film according to any one of 3. 【請求項５】 硬質炭素皮膜の厚さが０．５μｍ以上１
０μｍ以下であり、表面粗さがＲａ０．１μｍ以下でか
つ表面硬度がＨｖ１０００以上であることを特徴とする
請求項４に記載の硬質炭素皮膜摺動部材。5. A hard carbon film having a thickness of 0.5 μm or more
The hard carbon film sliding member according to claim 4, wherein the sliding member has a surface roughness of 0.1 µm or less and a surface hardness of Hv 1000 or more. 【請求項６】 金属元素の含有量が２５〜６０ａｔ％で
あり、硬質炭素皮膜の厚さが０．５μｍ以上１０μｍ以
下であり、表面粗さがＲａ０．１μｍ以下でかつ表面硬
度がＨｖ１０００以上であり、金属元素がモリブデン
（Ｍｏ）であって硬質炭素皮膜摺動部材を構成する硬質
炭素皮膜がイオンプレーティングにより作製されたダイ
ヤモンドライクカーボン膜（アモルファスカーボン膜）
であることを特徴とする請求項１に記載の硬質炭素皮膜
摺動部材。6. The metal element content is 25 to 60 at%, the thickness of the hard carbon film is 0.5 μm or more and 10 μm or less, the surface roughness is Ra 0.1 μm or less, and the surface hardness is Hv 1000 or more. There is a diamond-like carbon film (amorphous carbon film) in which the metal element is molybdenum (Mo) and the hard carbon film constituting the sliding member is formed by ion plating.
The hard carbon film sliding member according to claim 1, wherein: 【請求項７】 内燃機関の動弁機構のアジャスティング
シムあるいはバルブリフターに用いられることを特徴と
する請求項１ないし６のいずれかに記載の硬質炭素皮膜
摺動部材。7. The hard carbon film sliding member according to claim 1, which is used for an adjusting shim or a valve lifter of a valve mechanism of an internal combustion engine. 【請求項８】 鉱油および合成油を基油とし、モリブデ
ンジチオカーバメートをモリブデン量として５０〜１０
００ｐｐｍ，ジチオリン酸亜鉛をリン量として０．０１
〜０．２ｗｔ％含む潤滑油中で使用されることを特徴と
する請求項１ないし７のいずれかに記載の硬質炭素皮膜
摺動部材。8. A base oil comprising a mineral oil and a synthetic oil, and a molybdenum dithiocarbamate having a molybdenum content of 50 to 10
00 ppm, zinc dithiophosphate 0.01%
The sliding member according to any one of claims 1 to 7, wherein the sliding member is used in a lubricating oil containing up to 0.2 wt%. 【請求項９】 鉱油および合成油を基油とし、硫化油
脂，ポリサルファイド，硫化オレフィンなどのいおう
（Ｓ）系添加剤を含み、そのいおう（Ｓ）成分の含有量
が０．２ｗｔ％以上である潤滑油中で使用されることを
特徴とする請求項１ないし７のいずれかに記載の硬質炭
素皮膜摺動部材。9. Mineral oil and synthetic oil as base oils, containing sulfur (S) -based additives such as sulfurized fats and oils, polysulfides and sulfurized olefins, wherein the sulfur (S) component content is 0.2 wt% or more. The hard carbon film sliding member according to any one of claims 1 to 7, wherein the sliding member is used in a lubricating oil.
JP2000131750A 2000-04-28 2000-04-28 Hard carbon film sliding member Expired - Lifetime JP4007440B2 (en)

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